Phenylphosphonium salts

ABSTRACT

NOVEL PHENYLPHOSPHOIUM SALTS HAVE BEEN PREPARED. COMPOUNDS OF THIS INVENTION POSSESS USEFUL GASTRIC ANTISECRETORY, SPASMOLYTIC AND ANTI-ULCEROGENIC PROPERTIES. A METHOD OF TREATING GASTROINTESTINAL HYPERACIDITY AND ULCERATION HAS ALSO BEEN DISCLOSED.

United 'States Patent Ofice 3,755,459 PI-IENYLPHOSPHONIUM SALTS JuliusDiamond, Lafayette Hill., Pa., assignor to William H. Rorer, Inc.,Washington, Pa. N Drawing. Filed Jan. 22, 1971, Ser. No. 109,020 Int.Cl. C07f 9/54 US. Cl. 260-6065 F 22 Claims ABSTRACT OF THE DISCLOSURENovel phenylphosphonium salts have been prepared. Compounds of thisinvention possess useful gastric antisecrctory, spasmolytic andanti-ulcerogenic properties. A method of treating gastrointestinalhyperacidity and ulceration has also been disclosed.

SUMMARY OF THE INVENTION This invention describes new phosphonium saltsand processes for their preparation. This invention further providesvaluable pharmaceutical preparations which contain these phosphoniumsalts as gastric anti-secretory, spasmolytic, and anti-ulcerogenicagents. A method for the treatment of gastrointestinal hyperacidity andulceration is also described.

BACKGROUND OF THE INVENTION The pharmaceutical compositions which havebeen used as anti-secretory and spasmolytic agents have been such asatropine, homatropine, propantheline bromide, dicyclomine hydrochlorideaond other compounds which are structurally dissimilar to the oniurnsalts of this invention. Due to the anti-cholinergic properties of theseknown compounds, they produce undesirable side effects such asmydriasis, xerostomia, cyclopegia, and other unwanted effects.

There have been a number of aryl phosphonium salts described in theliterature. These have mainly been proposed for use as bactericidal andfungicidal agents, as well as plant growth regulators.

We have unexpectedly found novel phosphonium salts which have valuablepharmacologic properties.

We have found phosphonium salts which possess useful gastricanti-secretory, spasmolytic, and anti-ulcerogenic properties.

We have further found that the compounds of this invention aresubstantially void of the anti-cholinergic side effects which accompanyheretofore known gastric antisccretoryand spasmolytic agents.

We have also found a simple and efiective method for treating gastrichyperacidity and gastrointestinal ulceration such as duodenal pepticulcers.

DESCRIPTION AND PREFERRED EMBODIMENTS This invention provides a methodof preparing novel phosphonium salts.

This invention further provides pharmacologically active chemicalcompounds which are useful in treating gastrointestinal hyperacidity andulceration.

The compounds of this invention which are useful in treatinggastrointestinal hyperacidity and ulceration may be described by theGeneral Formula I:

R! I Ar-P -R A.-

I where:

Ar is an aryl as substitued aryl group; R, R and R" may be the same ordifferent and are a saturated or unsaturated acyclic member having up toPatented Aug. 28, 1973 12 carbon atoms, or a saturated or partiallyunsaturrated carbocyclic member having up to 12 carbon atoms; and

A is a non-toxic inorganic or organic anion.

More specifically, the compounds of this invention may be described bythe structural Formula II:

X Ill.

Y R. II

where:

X and Y may be the same or dilferent and are hydrogen, lower-alkyl,halo, haloloweralkyl, nitro, loweralkoxy, haloloweralkoxy, phenoxy,halophenoxy, phenyl or halophenyl;

R, R and R" may be the same or ditferent and are a 5 to 12 carbon atomsmember which may be straight chained or branched and are alkyl, alkenyl,cycloalkenyl or cycloalkylloweralkyl;

R may also be loweralkyl, loweralkenyl, loweralkynyl,

alkynyl, cycloalkenylloweralkyl, cycloloweralkyl,cycloloweralkylloweralkyl, arloweralkyl, polyfluoroloweralkyl,polyfluoroalkyl or substituted benzyl of the formula R3 Ra a s- JHwhere:

R, is hydrogen or loweralkyl;

The more preferred compounds of this invention are also the morepreferred compounds which are useful in treating gastrointestinaldisorders and diseases and are described by the structural Formula I:

where: I

X and Y are hydrogen, halo, haloloweralkyl, nitro or haloloweralkoxy;

R, R and R are a 5 to 12 carbon atom member which be straight chained orbranched and are alkyl or cycloalkyl;

R may also be arloweralkyl or substituted benzyl of the formula R5 whereR, is hydrogen or loweralkyl;

R R R R and R, are hydrogen, halo, haloloweralkyl,

nitro or haloloweralkoxy; and

A is chloride, bromide, iodide, nitrate, phosphate or sulfate.

The most preferred compounds of this invention embrace those compoundsof structural Formula II where X and Y are hydrogen, fluoro, chloro,bromo, trifluoromethyl, nitro or trifluoromethoxy;

R, R and R" are amyl, hexyl, heptyl, octyl, cycloamyl,

cyclohexyl, cycloheptyl or cyclooctyl;

R may also be benzyl or substituted benzyl of the formula I a e where:R, is hydrogen or methyl; and R R R R and R are hydrogen, fluoro,chloro, bromo,

trifluoromethyl, nitro or trifiuoromethoxy; and A is chloride, bromideor iodide.

A further more preferred embodiment of this invention embraces thosecompounds of Formula II where X and Y are hydrogen, halo,haloloweralkyl, nitro or haloloweralkoxy;

R and R are a 5 to 12 carbon atom member which may be straight chainedor branched and are: alkyl or cycloalkyl;

R is loweralkyl, loweralkenyl, loweralkynyl, cycloloweralkyl orcycloloweralkylloweralkyl;

A'- is chloride, bromide, iodide, nitrate, phosphate or sulfate.

The more preferred compounds of this latter embodiment are exemplifiedwhere X and Y are hydrogen, fiuoro, chloro, bromo, trifluoromethyl,nitro or trifiuoromethoxy;

R and R" are amyl, hexyl, heptyl, octyl, cycloamyl, cyclohexyl,cycloheptyl or cyclooctyl;

R is loweralkyl, loweralkenyl, loweralkynyl, cycloloweralkyl orcycloloweralkylloweralky;

A is choride, bromide or iodide.

In the descriptive portions of this invention, the following definitionsapply: The term lower alkyl refers to a lower alkyl hydrocarbon groupcontaining from 1 to 5 carbon atoms which may be straight chained orbranched.

The lower alkoxy radical signifies an alkoxy group containing from 1 to5 carbon atoms which can be straight chained or branched.

The compounds of this invention can contain an asymmetric phosphorousatom when R R' R" Ar. For this reason, they may be obtained as racemicmixtures or as dextor and levorotatory isomers. These may be separatedby any of the various methods of resolution to obtain the a or 1compound. These isomers may also be obtained via stereospecificcondensation reactions. It is understood that the optical isomers ofthese compounds are embraced Within the scope of this invention.

Representative compounds of this invention which are particularly usefulare as follows:

trioctylphenylphosphonium chloride trioctyl(p-fluorophenyl)phosphoniumchloride trioctyl(p-trifiuoromethyl)phosphonium chloridedioctylbenzylphenylphosphonium chloridedioctyKpfiuorobenzyl)phenylphosphonium chloride dioctylp-trifluoromethylbenzyl) phenylphosphonium chloridedioctylamylphenylphosphdnium chloride dihexylamylphenylphosphoniumchloride dioctyl(p-bromobenzyl)phenylphosphonium bromide dioctyl2,3,4,5,6-pentafiuorobenzyl phenylphosphonium chloridetriheptylphenylphosphonium chloride trihexylphenylphosphonium chloridetricyclohexylphenylphosphonium chloride tricycloheptylphenylphosphoniumchloride diheptyl(2,6-dichlorobenzyl)phenylphosphonium chloride dioctyl(2,6-dichlorobcnzyl) (p-chlorophenyl) phosphonium chloridedioctyl-(a-methylbenzyl) (p-chlorophenyl)phosphonuim chloridedihexylmethylphenylphosphonium chloride dihexylethylphenylphosphoniumchloride dihexylpropylphenylphosphonium chloride dihexyl (i-propyl)phenylphosphonium chloride dihexylbutylphenylphosphonium chloridedihexyl(i-butyl)phenylphosphonium chloride dihexyl s-butylphenylphosphonium chloride dihexyl (t-butyl) phenylphosphonium chloridedihexylpentylphenylphosphonium chloride dihexyloctylphenylphosphoniumchloride dihexylallylphenylphosphonium chloridedihexylmethallylphenylphosphonium chloridediheXyl(2-butenyl)phenylphosphonium chloride diheXyl(3-butenyl)phenylphosphonium chloride dihexyl(4pentenyl)phenylphosphonium chloridedihexyl (2,4-pentadienyl phenylphosphonium chloride dihexyl(2-propynyl)p-henylphosphonium chloride dihexylcyclopropylphenylphosphoniumchloride dihexylcyclopropylmethylphenylphosphonium chloridedihexylcyclopropylethylphenylphosphonium chloridedihexylcyclobutylphenylphosphonium chloridedihexylcyclobutylmethylphenylphosphonium chloridedihexylcyclopentylphenylphosphonium chloridedihexyl(Z-cyclopentenyl)phenylphosphonium chloridedihexylpropargylphenylphosphonium bromidedihexyl(Z-cyclohexenyl)phenylphosphonium chloridedihexylperfiuorobutylphenylphosphonium chloridedipentylallylphenylphosphonium chloride diheptylallylphenylphosphoniumchloride dicyclohexylallylphenylphosphonium chloridedicycloheptylallylphenylphosphonium chloridedicyclooctylallylphenylphosphonium chloridehexyloctylallylphenylphosphonium chlorideheptyloctylallylphenylphosphonium chloridecyclohexyloctylallylphenylphosphonium chloridecycloheptyloctylallylphenylphosphonium chloridecyclooctyloctylallylphenylphosphonium chloridetrioctyl(o-chlorophenyl)phosphonium chloride trihexyl(rn-chlorophenyl)phosphonium chloridetrihexyl(p-chlorophenyl)phosphonium chloridetrihexyl(2,3-dichlorophenyl)phosphonium chloride trihexyl(2,4-dichlorophenyl phosphonium chloride trihexyl (2,5-dichlorophenylphosphonium chloride trihexyl 2,6-dichlorophenyl )phosphoniurn chloridetrihexyl(3,4-dichlorophenyl)phosphonium chloridetriheXyl(3,5-dichlorophenyl)phosphonium chloride trihexyl(Z-bromophenyl) phosphonium chloridetrihexyl(3-bromophenyl)phosphoniumchloride triheXyl(4-bromophenyl)phosphonium chloride trihexyl(4-trifluoromethylphenyl)phosphoniumchloride trihexyl( i-nitrophenyl)phosphonium chloridetriheXyl(4-rnethoxyphenyl)phosphonium chloridedihexyl(o-chlorobenzyl)phenyl phosphonium chloridedihexyl(m-chlorobenzyl)phenyl phosphonium chloridedihexyl(p-chlorobenzyDphenyl phosphonium chloridedihexyl(2,3-dichlorobenzyl)phenyl phosphonium chloridedihexyl(2,4-dichlorobenzyl)phenyl phosphonium chloridedihexyl(2,5-dichlorobenzyl)phenyl phosphonium chloridedihexyl(2,6-dichlorobenzyl)phenyl phosphonium chloride dihexyl( 3,4-dichlorobenzyl) phenylphosphonium chloridedihexyl(3,S-dichlorobenzyDphenyl phosphonium chloridedihexyl(2,3,4-trichlorobenzyl)phenyl phosphonium chloride dihexyl( 2,3,5-trichlo robenzyl) phenyl phosphonium chloride The compounds of thisinvention may be prepared by the following general procedures:

Condensation of phosphorous trichloride with a molar amount of phenylorganometallic compound results in the phenyl dichlorophosphine. Furthercondensation with the proper organometallic reagents results in thetrisubstituted phosphine. Reaction of the trisubstituted phosphine withthe desired alkyl or aralkyl halide results in the correspondingquaternary phosphonium halide. [Phenyldichlorophosphines may also beprepared by the Michaelis modification of the Friedel-Crafts reaction asoutlined in JACS 73:755-6 (1951).]

The following reaction equal illustrates this method of synthesis:

Y R" Y Y II where X is chloride, bromide or iodide. When X or Y ischloro, then X is bromo or iodo but when X or Y is bromo, then X isiodo.

Phosphonium compounds having two similar groups are prepared by reactingthe phenyldichlorophosphine with two moles of Grignard reagent followedby condensation with the desired halide.

The above reactions may be carried out by the usual substitution processfor reactions involving organometallic reagents with halogen derivativesof trivalent phosphorous compounds.

One such method is by carrying out the reaction with one, two or threemoles of the desired organometallic reagent (preferably a Grignardreagent) in an inert medium such as ether, tetrahydrofuran, etc., andwith increased temperatures. Isolation may be carried out either bysubjecting the reaction mixture to vacuum distillation or by giving themixture a hydrolytic treatment with ammoniac chloride solution, followedby distillation of the organic layer.

Preparation of the phosphonium salts is preferably carried out with thephenyldisubstituted phosphine and a halide of the formula RX where R andX are as described above. The reaction is preferably carried out using asolvent and with increased temperatures. These reactions are alsopreferably carried out in an inert atmosphere under nitrogen or carbondioxide. The solvent used should be one that is miscible with thereactants and after it is convenient to use the reactant halide inexcess as the solvent or alternatively a high boiling polar medium suchas phenol, acetonitrile, dimethylformamide, dimethylsulfoxide,methylethylketone, etc. The reaction temperature may vary from roomtemperature with readily reactive reactants to about 250 0., although itis preferable to run the reaction at temperatures from about 50 C. to C.the isolation of the desired phosphonium halide can be carried out bydistilling off the solvent in vacuo and precipitating the phosphoniumhalide by the addition of a hydrocarbon liquid such as n-pentane,n-hexane, cyclohexane, etc.

Other anion salts can be produced by exchange of the halide with alkalior alkaline earth salts containing the appropriate anion.

When R is substituted benzyl, it is preferable to prepare thephosphonium compound on the phenyldisubstituted phosphine with thedesired benzyl halide.

x /R, R: Ra Ra P mQtHX Y RI! This reaction is conveniently carried outon the benzyl bromide or chloride using a solvent and increasedtemperatures. This synthesis is carried out and isolated as describedabove.

The benzyl halide starting materials can be conveniently prepared by thefollowing reactions.

R; R, R3

lHa0+ R R Ra R4 CH O R4 C O OH a n a u (d) l (where Ra=loweralkyl) (g)[LiAlH R3 1 Rd R3 R2 4- J=O R4 CH OH s s a a l l R3 R3 Ra R3 R1 R JHOH RCH X' 5 U B i Diazotizotization of an aromatic amine in the conven*tional manner followed by a Sandmeyer (a) type displacement produces thenitrile, which is then hydrolyzed (b) to the carboxylic acid. Rosenmundreduction (c) of the carboxylic acid results in the aldehyde which inturn is interacted with the desired alkyl Grignard reagent and oxidized(d) to obtain the a-alkylketone. This may then be reduced catalytically(e) to the a-alkylbenzyl alcohol. The alcohol is treated with aphosphorous trihalide, phosphorous oxyhalide, phosphorous pentahalide,thionylhalide or sulfuryl halide reagent (f) to obtain theoz-alkylbenzyl halide. Lithium aluminum hydride reduction of the benzoicacid (g) results in the benzyl alcohol which is then treated as above(f) to obtain the benzyl halide.

The phenyl Grignard reagents may be prepared from the correspondinganiline by conventional diazotization followed by a Sandmeyer typereaction using cuprous bromide or cuprous iodide to obtain the desiredphenyl halide which is then converted to the Grignard.

Appropriately desired end products having various X, Y, R R R R and Rsubstituents can be prepared at various stages of the synthesis of thestarting materials by using suitable reactions in order to convert onegroup to another. Thus, for example, using conventional methods, ahalogen group can be treated under Rosenmund Von Brown conditions to thenitrile compound which in turn can be hydrolyzed to a carboxy, A nitrocan be reduced to an amino which can be alkylated to the dialkylaminosubstituent. A hydroxy compound can be prepared by demethylation of amethoxy substituent. A Sandmeyer type reaction can be carried out on anamino compound to introduce a chloro, bromo, xanthate, hydroxyl oralkoxyl group. The xanthate can then lead to the mercapto by hydrolysis,this in turn can be alkylated to an alkylthio group which can beoxidized to alkylsulfinyl and alkylsulfonyl groups.

We have found that the compounds of this invention have usefulanti-ulcerogenic properties. Further, they have an effective degree ofgastric anti-secretory activity, i.e., they reduce the volume and theacidity of the gastric fluid in humans and mammals. Still further, thesecompounds produce a considerable spasmolytic action on thegastrointestinal musculature, i.e., they reduce the peristaltic actionof the gastrointestinal musculature which is manifested by a delay ingastric emptying time.

Until now, the known anti-ulcerogenic compounds which showed gastricanti-secretory and gastrointestinal spasmolytic action have includedsuch agents as atropine, hornatropine, propantheline, dicyclomine, etc.These compounds, however, cause accompanying undesirable anticholinergicproperties such as mydriasis, xerostomia, cyclopegia, etc.

We have found that the phosphonium compounds of this invention areparticularly useful as anti-secretory, antispasmodic and antiulcerogenicagents because they are essentially devoid of these unwanted effects.

In particular, the phosphonium compounds, as herein described, areuseful in the treatment of such gastrointestinal disorders and diseasesas duodenal ulcer and peptic ulcer.

For all of these purposes, the phonium compounds of this invention canbe administred orally or parenterally, but they are preferablyadministered orally. Orally they may be administered as tablets, aqueousor oily suspension, dispersible powders or granules, emulsions, hard orsoft capsules, or syrups or elixirsThe term parenteral, as used herein,includes subcutaneous injection, intramuscular injection or infusiontechniques.

Compositions intended for oral use may be prepared according to anymethod known to the art for the manufacture of pharmaceuticalcompositions and such compositions may contain one or more agentsselected from the group consisting of sweetening agents, flavoringagents, coloring agents and preserving agents, in order to provide apharmaceutically elegant and palatable preparation.

Further, these compounds may be tableted or otherwise formulated so thatfor every 100 parts by Weight of the composition, there are presentbetween 5 and parts of the active ingredient. The dosage unit form willgenerally contain between about 1 mg. and about 500 mg. of the activeingredients of this invention. The preferred unit dose is between about10 mg. and mg.

The dosage regimen in carrying out the methods of this invention is thatwhich insures maximum therapeutic response until improvement is obtainedand thereafter the minimum effective level which gives relief. Thus, ingeneral, the dosages are those that are therapeutically effective in thetreatment of ulcerogenic disease conditions or symptoms, such asduodenal and peptic ulcer. In general, the daily dose can be betweenabout 0.1 mg./kg. and 50 mg./kg. (preferably in the range of 1-25 mg./kg./ day). Bearing in mind, of course, that in selecting the appropriatedosage in any specific case, consideration must be given to the patientsweight, general health, age and other factors which may influenceresponse to the rug.

Various tests in animals have been carried out to show the ability ofthe compounds of this invention to exhibit reactions that can becorrelated with anti-ulcerogenic activity in humans. These tests involvesuch as the effect of the phosphonium compounds on gastric secretion,gastrointestinal spasm and their effect against ulcerogenic agents. Ithas been found that the compounds of this invention when tested in theabove variety of situations show a marked activity.

One such test is the gastric secretion test. This test is carried out asfollows: Shay rats are fasted for 4-8 hours, and water is given ad lib.The rats are selected at random and separated into groups of 10. Theanimals are treated intraduodenally (I.D.) with the test compound or thevehicle immediately subsequent to the ligation of the stomach at thepyloric sphinceter. The animals are sacrificed with chloroform at 4hours post-drug administration, the stomach is removed and its contentsare assayed for volume, pH and total acids.

A second gastric secretion test is carried out on dogs. This is outlinedin the Handbook of Physiology, Section 6: Alimentary Canal, volume II:Secretion, American Physiology Society, Washington, D.C., 1967.

It has been found that the compounds of this invention when subjected tothe above gastric secretion tests display a marked ability to decreasegastric volume and gastric acidity. These tests are known to correlatewell with gastric activity in humans and is a standard test used todetermine anti-secretory properties.

To determine the anti-ulcer effectiveness, the following test isemployed: Male Wistar rats (150 grams) are fasted for 24 hours, thengiven reserpine at 5 mg./kg. i.p. Twenty-four hours later, the stomachsare removed and examined for ulceration. Ulcers are graded on a 0-4scale and the number of ulcers is recorded. Pretreatment with thephosphonium compounds of this invention produces a decrease in ulcergrade and the number of ulcers compared to the control reserpine-treatedrats.

Determination of anti-spasmodic properties can be carried out by theprocedure as outlined by D. A. Brodie and S. K. Kundrats in theirarticle entitled Effect of Drugs n Gastric Emptying in Rats, Fed. Proc.24:714 (1965).

Mydriasis is detected by the procedure R. A. Turner, Screening Methodsin Pharmacology, Academic Press, New York and London, pp. 174-5, 1965.Acute toxicity is calculated according to the standardLitchfield-Wilcoxon procedure.

In view of the results of these tests, the pharmacological data clearlyindicates that the phosphonium compounds of this invention can beconsidered to be effective anti-ulcerogenic, anti-secretory, andanti-spasmodic agents which are substantially free of anti-cholinergicside elfects and having a low toxicity.

The following are detailed examples which show the preparation of thecompounds of this invention. They are to be construed as illustrationsof said compounds and not as limitations thereof.

EXAMPLE 1 Phenyldichlorophosphine To 83 g. (0.6 mole) of phosphoroustrichloride is added 27 g. (0.2 mole) of aluminum chloride and 13.8 g.(0.15 mole) of dry benzene. This reaction mixture is then gently heatedfor 2 hours with stirring over a blanket of nitrogen to expell theformed hydrogen chloride. The reaction mixture is then refluxed withvigorous stirring for an addi- .tional hour. The heat source is thenremoved and while the reaction mixture is still hot, phosphorousoxychloride 30.7 g. (0.2 mole) is gradually added. The mixture is thenallowed to cool to room temperature and extracted continuously withpetroleum ether for 2 hours. The petroleum ether extract is thenconcentrated in vacuo and distilled to obtain henyldichlorophosphine.

When benzene in the above example is replaced by the compounds of TableI below and the reaction product is fractionated then the correspondingproduct of Table II below is prepared.

Table I toluene ethylbenzene propylbenzene i-propylbenzenet-butylbenzene o-xylene m-xylene p-xylene biphenyl p-methylbiphenylanisole phenetole m-dimethoxybenzene trifiuoromethoxybenzene phenylether o-diethylbenzene Table II p-tolyldichlorophosphinep-ethylphenyldichlorophosphine p-propylphenyldichloropho sphinep-i-propylphenyldichlorophosphine p-t-butylphenyldichloropho sphine 3,4-dimethylphenyldichlorophosphine 2,4-dimethylphenyl) dichlorophosphine (2,5 -dimethylphenyl) dichlorophosphine (p-biphenyl)dichlorophosphine (p,p'-methylbiphenyl) dichlorophosphinep-methoxyphenyldichloropho sphine p-ethoxyphenyldichloropho sphine2,4-dimethoxyphenyldichlorophosphinep-trifluoromethoxyphenyldichlorophosphinep-phenoxyphenyldichlorophosphine 3,4-diethylphenyldichlorophosphineEXAMPLE 2 Dioctylphenylphosphine To a Grignard mixture ofn-octylmagnesium chloride (0.53 mole) prepared from 13.8 g. of magnesiumturnings and 78.4 g. of n-octyl chloride in 1300 ml. ether is added 31.2g. (0.175 mole) of phenyldichlorophosphine in ml. of ether with vigorousstirring and in a nitrogen atmosphere at 0 C. The reaction mixture isallowed to warm to room temperature over 2 hours. The mixture is thenpoured onto an ice-cold saturated solution of ammonium chloride (250ml.) and the mixture stirred for an additional hour. The aqueous layeris extracted with 2150 ml. portions of ether which is then combined withthe ether layer, dried over sodium sulfate, evaporated to dryness anddistilled to obtain dioctylphenylphosphine.

When n-octyl chloride in the above reaction is substituted with thehalides of Table I below, then the corresponding product of Table IIbelow is prepared.

Table I n-pentyl chloride n-hexyl chloride n-heptyl chloride n-nonylchloride n-decyl chloride n-undecyl chloride n-dodecyl chloride isoamylchloride Z-methyl-l-butenyl chloride cyclohex-2-enyl chloride cyclooctylchloride cycloheptyl chloride cyclopentyl chloride cyclohexyl chloridecyclohexylmethyl chloride 3,4,5-trimethylheptyl chloride 2-propylallylchloride 4-methyl-3-penten-1-yl chloride Z-methylheptyl chloride3-methylheptyl chloride 2-ethylhexy1 chloride 2,2,3,3-tetramethylbutylchloride cyclooct-Z-enyl chloride iso-octenyl chloride Table IIdipentylphenylphoshine dihexylphenylphosphine diheptylphenylphosphinedinonylphenylphosphine didecylphenylpho sphine diundecylphenylphosphinedidodecylphenylphosphine diisoamylphenylphosphine di 2-methyll-butenylphenylphosphine dicyclohex-Z-enyl phenylpho sphine dicyclooctylphenylphos phine dicycloheptylphenylphosphine dicyclop entylphenylphosphinedicyclohexylphenylphosphine diccyclohexylmethylphenylphosphine di- 3,4,5 -trimethylheptyl phenylphosphine di- (2-propylallyl phenylphosphinedi-(4-methyl-3-penten-1-yl)phenylphosphine di- (2-methylheptylphenylphosphine di- (3-methylheptyl phenylphosphine di- 2-ethylhexyl)phenylpho sphine di- 2,2,3 ,3-tetramethylbutyl) phenylphosphinedicyclooct-2-enyl phenylphosphine di- (iso-octenyl phenylphosphine 1 1EXAMPLE 3 When phenyldichlorophosphine in Example 2 is replaced by thephosphines of Table 11, Example I, then the corresponding product ofTable I below is prepared.

Table I dioctyl (p-tolyl )phosphine dioctyl (p-ethylphenyl phosphinedioctyl (p-propylphenyl phosphine diootyl (p-i-propylphenyl )pho sphinedioctyl(p-t-butylphenyl phosphine dioctyl(3,4-dimethylphenyl) phosphinedio ctyl (2, 4-dimethylphenyl phosphine dioctyl( 2,5 -dimethylphenylphosphine dio ctyl p-biphenyl )phosphine dioctyl (p,p'-methylphenylphosphine dioctyl (p-methoxyphenyl pho sphine dioctyl (p-ethoxyphenyl)phosphine dio ctyl (2,4-dimethoxyphenyl phosphine dioctyl(p-trifluoromethoxyphenyl pho sphine diocty1(phenoxypheny1)phosphinedioctyl 3 ,4-diethylphenyl) pho sphine EXAMPLE 4 When n-octylchloride inExample 2 is replaced with the halides of Table I, Example 2 and whenphenyldichlorophosphine is replaced with the phosphines of Table II,Example 1, then the corresponding tertiary phosphine is prepared. Arepresentative list of the compounds prepared is shown below in Table I.

Table I dipentyl (p-tolyl) phosphine dihexyl p-tolyl pho sphine diheptyl(p-tolyl) phosphine dinonyl(p-tolyl) phosphine diisoamyl(p-tolyl)phosphine di- (cyclohex-Z-enyl) (p-tolyl phosphine dicyclooctyl(p-tolyl) phosphine dicycloheptyl(p-tolyl phosphine dicyclohexyl(p-tolyl) phosphine dicyclohexylmethyl(p-tolyl) phosphine di-(2-propylallyl) (p-tolyl) phosphine di-(iso-octenyl) (p-tolyl) phosphinediheptyl(p-ethylphenyl) phosphine diheptyl( p-propylphenyl) phosphinediisoamyl(p-methoxyphenyl pho sphine di- (cyclohex-2-enyl)(p-ethylphenyl) phosphine dicyclohexylmethyl(p-t-butylphenyl )phosphinedinonyl (p-propylphenyl) phosphine di- (Z-ethylhexyl) (2,5-dimethylphenyl) phosphine dicycloheptyl (p-methoxyphenyl) phosphinediisoamyl (p-methoxyphenyl) phosphine di 2,2,3 ,3-tetramethylbutyl)(p-tolyl) phosphine di- (Z-methyl-l-butenyl) (p-tolyl)phosphinedidecyl(p-biphenyl) phosphine dipentyl (p-tolyDphosphinedi-(cyclooct-Z-enyl) (2,5-dimethylphenyl) phosphine di-(cyclohex-Z-enyl)(p-tolyl) phosphine dicyclohexylmethyl(p-ethoxyphenyl) phosphinedihexyl( 3,4-diethylphenyl) phosphine dicyclohexyl (2,4-dimethylphenyl)phosphine di-(iso-octenyl) (p-et-hoxyphenyl)phosphine di-(Z-propylallyl)(p-propylphenyl) phosphine dicyc1ooctyl( 3,4-dimethylphenyl phosphinedidodecyl(p-phenoxyphenyl) phosphine dicyclopentyl(p-trifluoromethoxyphenyl) phosphine diheptyl(p,p-methylbiphenyl)phosphine di-( 3,5 ,5 -trirnethylheptyl)(p-ethylphenyl )phosphine di-(4-methyl-3-penten-l-yl) (p-t0lyl)phosphinedi-(Z-methylheptyl) (p-methoxyphenyDphosphinediundecyl(p,p-methy1biphenyl)phosphine di- (S-methylheptyl) (p-tolylphosphine 12 EXAMPLE 5 Phenyldichlorophosphine To a Grignard mixture ofphenylmagnesium bromide (0.192 mole prepared from 5 g. of magnesiumtnrnings and 28.4 g. of bromobenzene in 600 ml. ether is added dropwisewith stirring 52.8 g. (0.384 mole) of phosphorous trichloride in 120 ml.of ether, in a nitrogen atmosphere at 0 C. The reaction mixture isallowed to warm to room temperature with stirring over 2 hours. Thisreaction mixture is filtered and the solid washed with 2-100 ml. ethercombined with the filtrate, concentrated in vacuo and distilled toobtain phenyldichlorophosphine.

When bromobenzene in the above example is replaced by the compounds ofTable I below, then the corresponding phosphine of Table 11 below isprepared.

Table I l-bromo-Zchlorobenzene 1-bromo-3-c-hlorobenzenel-bromo-4-chlorobenzene l-brom0-2,3-dich1orobenzene1-br0mo-3,5-dich1orobenzene Z-bromo-1,4-dichlorobenzene4-brom-o-l,Z-dichlorobenzene l-bromo-4-t-butylbenzene1-br0mo-2,3-dimethylbenzene l-bromo-2,4-dimethylbenzene4-bromo-1,2-dinitrobenzene 1-bromo-2-ethoxybenzene1-bromo-4-ethoxybenzene 1-bromo-4-fluorobenzene l-bromo-Z-iodobenzene1-br0mo-3-iodobenzene 1-bromo-4-iodobenzene 1-bromo-4-i-propylbenzene2-bromo-4-i-propyl-l-methylbenzene 1-bIomo-2-methoxybenzenel-bromo-Z-nitrobenzene 1-bromo-4-nitrobenzene 1-bromo-4-phenoxybenzenel-bromo-4-trifluoromethylbenzene 1-bromo-4-trifluoromethoxybenzenel-bromo-4-biphenyl l-bromo-4-phenoxybenzene 1-chloro-4-biphenyll,4'-dichlorobiphenyl l-chloro-4-methylbenzene1-ohloro-2,4-diethylbenzene l-iodo-2-methoxybenzene1-iod0-3-methoxybenzene l-iodo-4-methoxybenzene l-iodo-4-nitrobenzenel-iodo-2,4-dichlorobenzene 1-iodo-2,6-dichlorobenzene1-iodo-3,4-dichlorobenzene 1-iod0-4-trifluoromethylbenzene1-iodo-4-methylbenzene Table II (2-chlo1'ophenyl) dichlorophosphine (3-chlorophenyl) dichlorophosphine l-chlorophenyl) dichloropho sphine(2,3-dichlorophenyl dichlorophosphine (3 ,5 -dichlorophenyl)dichlorophosphine (3 ,4-dichlorophenyl) dichlorophosphine (4-t-butylphenyl) dichlorophosphine (2,3-dimethylphenyl )dichlorophosphine(2,4-dimethylphenyl) dichlorophosphlne (3 ,4-dinitrophenyldichlorophosphine Z-ethoxyphenyl) dichlorophosphine (4-etl1oxyphenyl)dichlorophosphine (4-fiuorophenyl dichlorophosphine (2-br0m0phenyl)dichlorophosphine (3-bromophenyl) dichlorophosphine (4-bromophenyl)dichloropho sphine (4-i-propylphenyl) dichlorophosphine(2-methyl-5-i-propylphenyl dichlorophosphine (Z-methoxyphenyl)dichlorophosphine (Z-nitrophenyl) dichlorophosphine (4-nitrophenyl)dichloropho sphine (4-phenoxyphenyl) dichlorophosphine(4-trifluoromethylphenyl) dichloropho sphine (4-trifluoromethoxyphenyl)dichlorophosphine (4-biphenyl) dichlorophosphine (4-phenoxyphenyl)dichloropho sphine (4,4'-chlorobiphenyl) dichlorophosphine(4-methylphenyl) dichlorophosphine (2,4-diethylphenyl) dichlorophosphine (3-methoxyphenyl dichloropho sphine (4-methoxyphenyl) dichlorophosphine (2,4-dichlorophenyl) dichlorophosphine (2,6-dichlorophenyl)dichlorophosphine EXAMPLE 6 Dihexylphenylphosphine To a Grignard mixtureof n-hexylmagnesium chloride (0.45 mole) prepared from 11.8 g. ofmagnesium turnings and 54 g. of n-hexylchloride in 1 l. ether is added31.2 g. (0.175 mole) of phenyldichlorophosphine in 100 ml. of ether withvigorous stirring and in a nitrogen atmosphere at C. The reactionmixture is allowed to warm to room temperature for 3 hours. The mixtureis poured onto a saturated ice-bath solution of ammonium chloride andthe mixture stirred for an additional half hour. The mixture isextracted three times with 300 ml. portions of ether. The ether is driedover sodium sulfate, evaporated to dryness and fractionated to obtaindihexylphenylphosphine.

When phenyldichlorophosphine in the above example is replaced by thephenylphosphine of Table H, Example 5, then the corresponding product ofTable I below is prepared.

Table I dihexyl 2-chlorophenyl) phosphine dihexyl (3-chlorophenylphosphine dihexyl (4-chlorophenyl phosphine dihexyl (2,3-dich1orophenyl) phosphine dihexyl( 3 ,5 -dichlorophenyl) phosphinedihexyl (3 ,4-dichlorophenyl) phosphine dihexyl (4-t-butylphenyl) phosphine dihexyl (2,3-dimethylphenyl phosphine dihexyl (2,4-dimethylphenylphosphine dihexyl( 3 ,4dinitrophenyl pho sphine dihexyl (2-ethoxyphenylphosphine dihexyl (4-ethoxyphenyl phosphine dihexyl (4-fluorophenyl) phosphine dihexyl (2-bromophenyl) phosphine dihexyl (3-bromopheny1phosphine dihexyl (4-bromophenyl phosphine dihexyl (4-i-propylphenyl)pho sphine dihexyl (Z-methyl-S-i-propylphenyl phosphine dihexylZ-methoxyphenyl phosphine dihexyl (2-nitrophenyl pho sphine dihexyl(4-nitrophenyl) pho sphine dihexyl (4 phenoxyphenyl phosphine dihexyl(4-trifluoromethylphenyl phosphine dihexyl (4-trifluoromethoxyphenyl)pho sphine dihexyl (4-biphenyl) phosphine dihexyl (4-phenoxyphenyl phosphine dihexyl (4,4'-chlorobiphenyl phosphine dihexyl (4-methylphenylphosphine dihexyl (2,4-diethylphenyl) phosphine dihexyl(3-methoxyphenyl) phosphine dihexyl 4-methoxyphenyl pho sphine dihexyl2,4-dichlorophenyl) phosphine dihexyl (2,6 -dichloropheny1 pho sphine 14EXAMPLE 7 Hexylphenylc-hlorophosphine To a Grignard mixture ofhexylmagnesium chloride (0.1 mole) prepared from (2.6 g. of magnesiumturnings and 16.3 g. of hexylbromide in 300 ml. of ether) is addeddropwise to an inert atmosphere with stirring and at 0 C., 43 g. (0.15mole) of phenyldichlorophosphine in 75 ml. of ether. The reactionmixture is stirred over 1% hours and allowed to gradually warm to roomtemperature. The reaction mixture is then filtered, residue washed withether combined with the filtrate and concentrated in vacuo and distilledto obtain hexylphenylchlorophosphine.

When hexylbromide in the above reaction is replaced with the halides ofExample 2, then the corresponding phoshpine of Table 1', below isprepared.

Table I pentylphenylchlorophosphine heptylphenylchlorophosphineoctylphenylchlorophosphine nonylphenylchlorophosphinedecylphenylchlorophosphine undecylphenylchlorophosphinedodecylphenylchlorophosphine isoamylphenylchlorophosphine(Z-methyl-1-butenyl)phenylchlorophosphine (cyclohex-Z-enylphenylchlorophosphine cyclo0ctylphenylchlorophosphinecycloheptylphenylchlorophosphine cyclopentylphenylchlorophosphinecyclohexylphenylchlorophosphine cyclohexylmethylphenylchlorophosphine(3,4,5 -trimethylheptyl) phenylchlorophosphine (2-propylallylphenylchlorophosphine (4-methyl-3-penten-1-yl) phenylchlorophosphine(2-methylheptyl) phenylchlorophosphine 3 -methylhep tyl)phenylchlorophosphine (2-ethylhexyl)phenylchlorophosphine (2,2,3,3-tetramethylbutyl phenylchlorophosphine (cyclooct-Z-enyl)phenylchlorophosphine (iso-octenyl) phenylchlorophosphine EMMPLE '8 Whenphenyldichlorophosphine of Example 7 is replaced with thephenyldichlorophosphines of Table II, Example 1 and Table II, Example 5,then the corresponding phosphines of Table 1, below are prepared.

Table I hexyl 2-chlorophenyl) chlorophosphine hexyl (3 -chlorophenyl)chlorophosphine hexyl (4-chlorophenyl chlorophosphine hexyl 2, 3-dichl0rophenyl) chlorophosphine hexyl 3, S-dichlorophenylchlorophosphine hexyl (3 ,4-dichlorophenyl) chloropho sphine hexyl4-t-butylphenyl) chlorophosphine hexyl (2,3 -dimethylphenylchlorophosphine hexyl (2,4-dimethylphenyl) chloropho sphinehexyl(3,4-dinitropheny1)chlorophosphine hexy1(2-ethoxyphenyl)chlorophosphine hexyl (4-ethoxyphenyl chloropho sphine hexyl(4-fluorophenyl) chlorophosphine hexyl 2-brom0phenyl) chlorophosphinehexyl (3-bromophenyl) chloropho sphine hexyl 4-bromophenyl)chlorophosphine hexyl (4-i-propylphenyl) chlorophosphine hexylZ-methyl-S-i-propylphenyl chlorophosphine hexyl Z-methoxyphenyl)chloropho sphine hexyl Z-nitrophenyl) chlorophosphine hexyl(4-nitrophenyl) chloropho sphine hexyl (4-phenoxyphenyl) chlorophosphineh'exyl(4-t1iflu0romethylphenyl)chlorophosphine hexyl4-trifluoromethoxyphenyl) chloropho sphine hexyl(4-biphenyl)chlorophosphine hexyl (4-phenoxyphenyl chloropho sphine hexyl4,4'-chlorobiphenyl) chlorophosphine hexyl(4-methy1phenyl chlorophosphine hexyl (2,4-diethylphenyl chlorophosphine hexyl 3-methoxyphenylchlorophosphine hexyl 4-methoxyphenyl) chlorophosphine hexyl2,4-dichlorophenyl) chlorophosphine hexyl( 2, 6-dichloropheny1)chloropho sphine hexyi p-ethylphenyl chlorophosphine hexylp-propylphenyl chlorophosphine hexyl( 2,4-dimethylphenyl chloro pho sphine hexyl (2, 5 -dimethyl phenyl) chlorophosphine hexy1(3,4-diethylphenyl) chlor ophosphine EXAMPLE 9 Whenphenyldichlorophosphine of Example 7 is replaced with thephenyldichlorophosphines of Table II, Example 1 and Table II, Example 5and when hexyl chloride is replaced with the halides of Table I, Example2, then the corresponding disubstituted phosphine is prepared. Arepresentative list of the compounds prepared is shown in Table I,below.

Table I pentyl 2-chlorophenyl chlorophosphine heptyl (2-nitrophenyl)chlorophosphine cyclooctyl Z-brornophenyl) chlorophosphine cyclohexyl(2-chlorophenyl chlorophosphine 2-methyl-1-butenyl 2-ethoxypehnylchlorophosphine cyclohexyl (3 ,5 -dich1orophenyl) chlorophosphinecycloheptyl (Z-methoxyphenyl) chlorophosphine decyl( 3 -methoxyphenylchlorophosphine cyclohexyl 3-bromophenyl) chlorophosphine cyclohexyl(3-chlorophenyl chloropho sphine cyclohex-Z-emyl) (4-methoxyphenyl)chlorophosphlne iso-octenyl) (4-phenoxyphenyl) chlorophosphine pentyl4trifluoromethylphenyl chlorophosphine cyclohexylmethyl (4-bromophenyl)chlorophosphine Z-ethylhexyl) (4-t-butylphenyl chlorophosphine(cyclooct-Z-enyl) (4-ethoxyphenyl chlorophosphine cycloheptyl(4-fluorophenyl) chlorophosphine nonyl 4-i-propylphenyl) chlorophosphine(Z-methylheptyl) (4-nitrophenyl) chlorophosphine cyclopentyl(4-chloropl1enyl chloropho sphine (3-methylheptyl)(2,3-dimethy1phenyl)chlorophosphine isoamyl (2,3-dichlorophenylchlorophosphine (4-methyl-3 -penten-1-yl) (4-trifluoromethoxyphenyl)chlorophosphine unde cyl (4-rnethylphenyl) chloropho sphine isoamyl 3,4-diethylphenyl) chloropho sphine cyclohexyl (2,4dimethylphenyl)chlorophosphine (2,2,3 ,3-tetramethylbutyl) (4-phenoxyphenyl)chlorophosphine (2-propylallyl) (4-biphenyl) chlorophosphine cyclohexyl(3 ,4-diehlorophenyl) chlorophosphine cyclohexylmethyl 2,4-diethylphenyl)chlorophosphine isoamy1(2,5-dimethylphenyl chlorophosphine cyclopentyl(2,4-dimethylphenyl) chlorophosphine do decyl (2-methyl-5-i-propylphenyl) chlorophosphine isoamyl (p-propylphenyl)chlorophosphine pentyl (2,6-dichloropheny1) chlorophosphine cyclohexyl2,4-dichlorophenyl chlorophosphine (3 ,4,5-trimethylheptyl) (3,4-dinitrophenyl) chlorophosphine cyclohexyl (4,4'-chlorobiphenyl)chlorophosphine EXAMPLE 1O Hexyloctylphenylphosphine To a Grignardmixture of octylmagnesium bromide (0.075 mole) in 250 ml. of ether isadded dropwise with stirring 28.5 g. (0.125 mole) ofhexylphenylcblorophosphine in 75 ml. of ether at 0 C. The reaction iscarried out under nitrogen and vigorously stirred for 2 hours. Thetemperature is allowed to gradually warm up to room temperature. Thereaction mixture is then poured onto an ice-cold saturated solution ofammonium chloride (300 ml.) and the mixture stirred for one hour. Theaqueous layer is extracted with 200 ml. of ether combined with the etherlayer, dried over sodium sulfate, evaporated to dryness and distilled togive hexyloctylphenylphosphine.

When the octylmagnesium bromide of the above reaction is replaced Withthe Grignard reagents of the halides of Table I, Example 2, then thecorresponding tertiary phosphine of Table I below is prepared.

pentylhexylphenylphosphine dihexylphenylphosphineheptylhexylphenylphosphine nonylhexylphenylphosphine decylhexylphenylphosphine undecylhexylphenylpho sphine dodecylhexylphenylphosphineisoamylhexylphenylpho sphine (2-methyl-1-butenyl) hexylphenylphosphine(cyclohex-2-enyl hexylphenylphosphine cyclooctylhexylphenylphosphinecycloheptylhexylphenylphosphine cyclop entylhexylphenylphosphinecyclohexylhexylphenylphosphine cyclohexylmethylhexylphenylphosphine (3,4, 5 -trimethylheptyl hexylphenylphosphine (Z-propylallylhexylphenylphosphine (4-methyl-3 -pentenl-yl) hexylphenylphosphine(Z-methylheptyl) hexylphenylphosphine (3 -methylheptyl)hexylphenylphosphine (2-ethylhexyl) hexylphenylphosphine(2,2,3,3-tetramethylbutyl) hexylphenylphosphine (cyclooct-Z-enylhexylphenylphosphine iso-octenylhexylphenylpho sphine EXAMPLE 1 1 Whenhexylphenylchlorophosphine of Example 10 is replaced by thechlorophosphines of Table 1, Example 7, then the corresponding tertiaryphosphine of Table I below is prepared.

Table I octylpentylphenylphosphine 0ctylheptylphenylphosphinedioctylphenylphosphine octylnonylphenylphosphineoctyldecylphenylphosphine octylundecylphenylphosphineoctyldodecylphenylphosp hine octylisoamylphenylpho sphine octyl(2-methyll-butenyl) phenylphosphine octyl (cyclohex-Z-enyl) phenylphosphine octylcy clooctylphenylpho sphine octylcycloheptylphenylphosphineoctylcyclopentylphenylphosphine octylcy clohexylphenylphosphineoctylcyclohexylmethylphenylphosphine octyl( 3 ,4,5-trimethylheptyl)phenylphosphine octyl (2-propylallyl phenylphosphine octyl4-methyl-3-penten-l -yl) phenylphosphine octyl Z-methylheptylphenylphosphine octyl 3-methylheptyl) phenylphosphine octyl 2,2, 3 ,3-tetramethylbutyl) phenylphosphine octyl cyclooct-Z-enyl)phenylphosphine octyl (iso-octenyl) phenylpho sphine EXAMPLE 12 Whenhexylphenylphosphine of Example 10 is replaced by the chlorophosphinesof Table I, Example 8, then the corresponding tertiary phosphine ofTable I, below is prepared,

Table I octylhexyl (2-chlorophenyl) phosp hine octylhexyl3-chlorophenyl) phosphine octylhexyl (4-chlorophenyl phosphineoctylhexyl (2,3 -dichlorophenyl phosphine octylhexyl 3 ,5-dichlorophenyl phosphine octylhexyl( 3 ,4-dichlorophenyl) phosphineoctylhexyl (4-t-butylphenyl) phosphine octylhexyl (2,3-dimethylphenyl)phosphine octylhexyl (2,4- dimethylphenyl phosphine octylhexyl (3,4-dinitrophenyl) phosphine octylhexyl Z-ethoxyphenyl) pho sphineoctylhexyl 4-ethoxyphenyl) phosphine octylhexyl (4-flu orophenyl phosphine octylhexyl (2-bromophenyl phosphine octylhexyl (2-bromophenylphosphine octylhexyl 3 -bromophenyl) phosphine octylhexyl 4-bromophenyl)phosphine octylhexyl(4-i-propylpheny1)phosphine octylhexylZ-methyl-S-i-propylphenyl phosphine octylhexyl (2-methoxyphenyl)phosphine octylhexyl (2-nitrophenyl) phosphine octylhexyl (4-nitrophenylphosphine octylhexyl (4-phenoxyphenyl pho sphine octylhexyl(4-trifluoromethylphenyl) pho sphine octylhexyl4-trifiuoromethoxypheny1) phosphine oetylhexyl 4-biphenyl phosphineoctylhexyl (4-phenoxyphenyl )phosphine octylhexyl 4,4'-chlorobiphenylphosphine octylhexyl (4-rnethylphenyl )pho sphine octylhexyl(2,4-diethylphenyl phosphine octylhexyl S-methoxyphenyl) pho sphineoetylhexyl (4-methoxyphenyl pho sphine octylhexyl (2,4-dichlorophenyl)phosphine octylhexyl (2,6-dichlorophenyl phosphine octylhexyl(p-ethy1phenyl)phosphine octylhexyl (p-propylphenyl pho sphineoctylhexyl 2-methyl-4-bromophenyl phosphine octylhexyl (2,5-dimethylphenyl pho sphine octylhexyl (2,5 -dimethylphenyl) phosphineoctylhexyl (p-bromopheuoxyphenyl) pho sphine EXAMPLE 13 Whenoctylmagnesium bromide of Example 10 is replaced by the Grignard reagentof the halides of Table I, Example 2 and hexylphenyl-chlorophosphine isreplaced by the chlorophosphines of Table I, Example 9, then thecorresponding representative tertiary phosphines of Table I below areprepared.

Table I pentyl (4-phenoxyphenyl) hexylphosphine pentyl(4-trifluorornethylphenyl hexylphosphine pentyl(4-trifluoromethoxyphenyl) hexylphosphine pentyl (4-biphenylhexylphosphine pentyl (4-phenoxyphenyl )hexylphosphinepentyl(4,4-chlorobiphenyl)hexylphosphine pentyl 4-methylphenyl hexylphosphine pentyl (2,4-diethylpheny1) hexylphosphine pentyl 3-methoxyphenyl)hexylpho sphine pentyl (4-methoxyphenyl )hexylpho sphine pentyl(2,4-dichlorophenyl) hexylphosphine pentyl (2,6-dichlorophenyl)hexylphosphine heptyl Z-nitrophenyl) isoamylphosphinecyclooctyl(2-bromophenyl pentylphosphine cyclohexyl (2-chlorophenyl)undecylphosphine (Z-methyl-l-butenyl) (Z-ethoxyphenyl) (2-ethylhexyl)phosphine cyclohexyl 3,5 -dichlorophenyl) hexylphosphinecycloheptyl(Z-methoxyphenyl) (3-methylheptyl) phosphine decyl3-methoxyphenyl) pho sphine cyclohexyl 3-bromophenyl pentylphosphinecyclohexyl 3-chlorophenyl) (cyclohex-Z-enyl) phosphine(cyclohex-2-enyl)(4-rnethoxypheuyDphosphine (iso-octenyl)(4-phenoxyphenyl) cyclooctylphosphine isoamyl (4-trifluoromethylphenyl)(2-methyll-butenyl) phosphine cyclohexylmethyl (4-bromophenyl)(2-methylheptyl) phosphine (Z-ethylhexyl) 4-t-butylphenylheptylphosphine (cyclooct-2-enyl) (4-ethoxyphenyl) (4-methyl-3-penten-1-yl)phosphine cycloheptyl(4-fluorophenyl)isoamylphosphine nonyl(4-i-propylphenyl octylphosphine (Z-methylheptyl)(4-nitrophenyl)cycloheptylphosphine dicyelopentyl (4-chlorophenyl)phosphine (3-methylheptyl) (2,3-dimethylphenyl)isoamylphosphine isoamyl(2,3-dichlorophenyl cyclohexylphosphine (4-methyl-3 -penten-1-yl)(4-trifluoromethoxyphenyl) cyclohexylmethylphosphine undecyl(4-methylphenyl nonylphosphine isoamyl (4-i-propylphenyl) phosphinecyclohexyl (2,4-dimethylphenyl) decylphosphine (2,2, 3, 3-tetramethylbutyl) (4-phenoxyphenyl) cyclohexylphosphine 2-propylallyl)4-biphenyl) dodecylphosphine cyclohexyl 3,4-dichlorophenyl)(2,2,3,3-tetramethylbutyl)phosphine cyclohexylmethyl (2,4-diethylphenyl)isoamylphosphine isoamyl(2,5-dimethylphenyl) (3,4,S-trimethylheptyl)phosphine cyclopentyl (2,4-dimethylphenyl) (2-propy1al1yl) phosphinedodecyl (Z-methyl-5-i-propylphenyl cyclohexylphosphineisoamy1(p-propylphenyl) (cyclooct-Z-enyl) phosphine cyclohexyl 2,6-dichlorophenyl isoamylphosphine cyclohexyl 2,4-dichlorophenyl)(iso-octenyl) phosphine (3 ,4, 5 -trimethylheptyl) (3,4-dinitrophenyl)pentylphosphine cyclohexyl (4, 4-chlorobiphenyl) isoamylphosphineEXAMPLE 14 Hexyloctylpentylphenylphosphonium chloride To 76.5 g. (0.25mole) of hexyloctylphenylphosphine in 500 ml. of acetonitrile is added28.6 g. (0.27 mole) of pentyl chloride. The mixture is refluxed for 15hours, concentrated in vacuo and the residue agitated with 3-200 ml.portions of hexane. The hexane is evaporated to givehexyloctylpentylphenylphosphonium chloride.

When the procedure is followed but phenyl chloride is substituted forthe halides of Table I below, then the corresponding product isprepared.

1 9 Table I methyl iodide ethyl bromide propyl bromide i-propyl bromidebutyl bromide i-butyl chloride sec-butyl chloride t-butyl bromide allylbromide methallyl chloride 1-bromo-2,4-pentadiene Z-butenyl bromide4-pentenylbromide l-propynyl chloride propargyl bromide S-hexynylchloride cyclohex-Z-enylmethyl chloride 1-bromo-2,4-cyclopentadienecyclopropyl bromide cyclobutylbromide Z-methylcyclopropyl bromidecyclopropylmethyl chloride Z-ethylcyclopropylmethyl chloridecyclobutylmethyl bromide pentafluoroethy chloride5,5,5-trifluoro-l-bromopentane 3,3,3-trifiuoro-l-bromopropane EXAMPLE 15When the procedure of Example 14 is followed but pentyl chloride isreplaced by the halides of Table I, Example 2 and Table I, Example 14and the hexyloctylphenylphosphine is replaced by the tertiary phosphinesof Examples 2, 3, 4, 6, 10, 11, 12, and 13, then the correspondingphosphonium salt is prepared. A representative list of the phosphoniumsalts prepared is shown in Table 1, below.

Table I dipentylcyclohexylphenylphosphonium chloridedihexylpentylphenylphosphonium chloride diheptyl-i-amylphenylphosphoniumchloride trinonylphenylphosphonium chloride tridecylphenylphosphoniumchloride diisoamylhexylphenylphosphonium chloridedicycloheptylheptylphenylphosphonium chloridedicyclopentylcycloheptylphenylphosphonium chloridedicyclohexyl(Z-ethylhexyl)phenylphosphonium chloridedicyclohexylmethyl(t-butyl)phenylphosphonium bromide di-(2-propylallyl)methylphenylphosphonium iodidedi-(4-methyl-3-penten-1-yl) (4-pentenyl)phenylphosphonium bromidedi-(cycloocg-Z-enyl)methylphenylphosphonium iodidedi-(iso-octenyl)ethylphenylphosphonium bromidetrioctyl(p-tolyl)phosphonium chloride dioctyl (i-propyl) (p-ethylphenyl)phosphonium bromide dioctyl(3-methylheptyl) (p-bromophenyl)phosphoniumchloride dioctylallyl(p-chlorophenyDphosphonium bromidedioctylallyl(p-nitrophenyl)phosphonium bromide dioctyl(2-propylallyl)(2-methyl-4-bromophenyl) phosphonium chloridedioctylcyclopropylmethyl(p-biphenyDphosphonium chloridedioctyl(5-hexynyl) (p-methoxyphenyl)phosphonium chloride dioctylhexyl(phenoxyphenyl)phosphonium chloridedipentyl-t-butyl(p-chlorophenyl)phosphonium bromidedihexylallyl(p-chlorophenyl)phosphonium bromide diheptyl-i-propyl(p-chlorophenyl)phosphonium bromidediisoamylhexyl(p-chlorophenyl)phosphonium chloride dicycloheptyl-i-amyl(p-chlorophenyl) phosphonium chloridedicyclohexylhexyl(p-chlorophenyl)phosphonium chloridedihexylpropargylphenylphosphonium bromide dicyclohexylmethyl (hexyl)(p-chlorophenyl) phosphonium chloridedi-(Z-propylallyl)-i-butyl(p-chlorophenyl) phosphonium chloridediheptylheXyl(p-tolyl) phosphonium chloride diheptylamyl (p-nitrophenyl)phosphonium chloride triisoarnyl(p-methoxyphenyl)phosphonium chloridetricyclohexylmethyl (p-bromophenyl) pho sphonium chloride tricycloheptyl(p-trifluoromethylphenyl phosphonium chloridediisoamylhexyl(p-methoxyphenyl)phosphonium chloride tripentyl(p-tolyDphosphonium chloride trihexyl(p-bromophenyl)phosphonium bromidetricyclopentyl(p-trifluoromethoxyphenyl)phosphonium chloride heptyl(p,p'-chlorobiphenyl)phosphonium chloride di- (Z-methylheptyl hexyl(p-methoxyphenyl) phosphonium chloridedihexyloctyl(Z-chlorophenyl)phosphonium chloride dihexylpentyl(3-chlorophenyl phosphonium chloridedihexylpentyl(4-chlorophenyl)phosphonium chloridedihexylpentyl(2,3-dichlorophenyl)phosphonium chloridetrihexyl(3,5-dichlorophenyl) phosphonium chloride dihexylheptyl3,4-dichlorophenyl phosphonium chloridedihexylisoamyl(4-t-butylphenyl)phosphonium chloridedihexylpropyl(2,4-dimethylphenyl(phosphonium bromidedihexylmethallyl(Z-ethoxyphenyDphosphonium chloridetrihexyl(4-ethoxyphenyl)phosphonium chloridetrihexyl(4-fiuorophenyl)phosphonium chloridedihexylcyclopropyl(Z-bromophenyl)phosphonium bromidedihexylcyclobutylmethyl(3-bromophenyl)phosphonium bromidedihexyloctyl(4-bromophenyl) phosphonium chloridediheXyl-i-propyl(4-i-propylphenyl)phosphonium bromidetrihexyl(Z-methyl-S-i-propylphenyl)phosphonium chloride dihexyl2,4-pentadienyl) (Z-methoxyphenyl)phosphonium bromidedihexylmethallylphenylphosphonium chloridedihexylheptyl(2-nitrophenyl)phosphonium chloridetrihexyl(4-nitrophenyl)phosphonium chloridetrihexyl(4-phenoxyphenyl)phosphonium chloride dihexyl(3,3,3-trifluoropropyl) (4-trifluoromethylphenyl) phosphonium bromidetrihexyl(4-biphenyl)phosphonium chloride dihexyl-t-butyl(4-methylphenyl)phosphonium bromide dihexylethyl(2,4-diethylphenyl)phosphonium bromidedihexylcyclobutyl(3-methoxyphenyl)phosphonium bromidetriheXyl(4-methoxyphenyl) phosphonium chloridetrihexyl(2,4-dichlorophenyl)phosphonium chloridetriheXyl(2,6dichlorophenyl)phosphonium chloridepentylheptylhexylphenylphosphonium chlorided1hexyl-t-butylphenylphosphonium chlorideheptylhexylmethallylphenylphosphonium chloridenonylhexylallylphenylphosphonium chloridedecylethylhexylphenylphosphonium chlorideundecylcyclopropylhexylphenylphosphonium chloridedihexyldodecylphenylphosphonium chlorideisoamylethylhexylphenylphosphonium chloride(Z-methyl-1-butenyl)-i-propylhexylphenylphosphonium bromidecyclohex-Z-enyl pentylhexylphenylphosphonium chloridecyclooctylheptylhexylphenylphosphonium chloridecycloheptylpentylhexylphenylphosphonium chloridecyclopentylpentylhexylphenylphosphonium chloridedicyclohexylhexylphenylphosphonium chloridedicyclohexylmethylhexylphenylphosphonium chloride(3,4,5-trimethylheptyl)methylhexylphenylphosphonium iodide(2-propylallyl)hexylmethylphenylphosphonium iodide(4-methyl-3-penten-l-yl)hexylpentylphenylphosphoniumchloridedihexyl(2-butenyl) phenylphosphonium bromide(Z-methylheptyl)hexylisoamylphenylphosphonium chloride(3-methylheptyl)hexyl(2-propylallyl)phenylphosphonium chloride(Z-ethylhexyl) hexylcyclohexylphenyl) phosphonium chloride(2,2,3,3-tetramethylbutyl)hexylpropylphenylphosphonium bromide(cyclooct-Z-enyl)hexylisoamylphenylphosphonium chlorideiso-octenylhexylcyclohexylphenylphosphonium chlorideoctylpentylisoamylphenylphosphonium chlorideoctylcyclopentylheptylphenylphosphoniurn chloridedioctylmethylphenylphosphonium chloride dioctylisoamylphenylphosphoniumchloride octyl(2-methyl-1-butenyl) propylphenylphosphonium bromideoctyl(cyclohex-Z-enyl)-i-butylphenylphosphonium chlorideoctylcyclooctyl(iso-octenyl)phenylphosphonium chlorideoctylcyclopentylpropargylphenylphosphonium chlorideoctylmethylcycloheXylmethylphenylphosphonium iodide octyl (2-propylallylpropargylphenylphosphonium chloride dioctyl(4-methyl-3-penten-l-yl)phenylphosphonium chlorideoctylhexylpropyl(4-chlorophenyl)phosphonium bromide octylhexyl(Z-ethylhexyl) (2,3-dich1orophenyl) phosphonium chlorideoctylhexyl-t-butyl(4-t-butylphenyl)phosphonium chlorideoctylhexylpropynyl (2,3-dimethylphenyl) pho sphonium chlorideoctylhexylcyclobutylmethyl (2,4-dimethylphenyl phosphonium chlorideoctylhexylmethyl) Z-ethoxyphenyDphosphonium iodide octlhexylpentafluoroethyl (4-fluorophenyl) pho sphonium chlorideoctylhexyl-i-butyl(Z-bromophenyl)phosphonium chloridedioctylhexyl(4-bromophe11yl)phosphonium chlorideoctylhexyl(2,4-cyclopentadien-l-yl) (4-i-propylphenyl) phosphoniumchloride octylhexylcyclobutyl (Z-methoxyphenyl phosphonium chlorideoctylhexyl(2-methylcyclopropyl) (4-nitrophenyl)phosphonium chlorideoctylhexylpropyl(4-trifluoromethylphenyl)phosphonium bromide dihexyl(2,4-cyclop entadienl-yl) phenylphosphonium bromideoctylhexyKZ-ethylhexyl) (4-methoxyphenyl)phosphonium chlorideoctylhexylcyclohexyl(2,4-dichlorophenyl)phosphonium chlorideoctylhexyl-i-propyl (p-propylphenyl) phosphonium bromidepentyl-i-propyl(2-chlorophenyl)hexylphosphonium bromidepentyl-i-propyl(4-chlorophenyl)hexylphosphonium bromidepentylisoamyl(3,5-dichlorophenyl)hexylphosphonium chloridepentyl-t-butyl(3.4-dichlorophenyl)hexylphosphonium bromidepentyl(pentenyl) (4-t-butylphenyl)hexylphosphonium chloridepentyl(Z-methylcyclopropyl) (2,4-dimethylphenyl)hexylphosphoniumchloride dipentyl(4-ethoxyphenyl)hexylphosphonium chloridepentylpropyl(4-fluorophenyl)hexylphosphonium bromidepentyl-sec-butyl(2-bromophenyl)hexylphosphoniurn chloridedipentyl(4-i-propylphenyl)hexylphosphonium chloridepentylisoamyl(4-nitrophenyl)hexylphosphonium chloridepentylmethyl(4-trifluoromethylphenyl)hexylphosphonium iodide pentyl(cyclohex-Z-enylmethyl) (4-methylphenyl)hexy1- phosphonium chloridepentyl (Z-ethylcyclopropylmethyl) (4-methoxyphenyl) hexyl phosphoniumchloride dipentyl(2,4-dichlorophenyl)hexylphosphonium chloridepentyl(3,3,3-trifluoropropyl) (2,6-dichlorophenyl)hexyl phosphoniumchloride dicyclooctyl(Z-bromophenyl)pentylphosphonium chloride(Z-methyl-l-butenyl) (Z-ethylcyclopropylmethyl) (2- ethoxyphenyl)(2-ethylhexyl)phosphonium chloridedicyclohexyl(3,5-dichlorophenyl)hexylphosphonium chloridedicyclohexyl(3-brornophenyl)pentylphosphonium chloride (cyclohex-2-enyl)ethyl (4-methoxyphenyl) phosphonium bromidediisoamyl(4-trifluoromethylphenyl) (Z-methyl-l-butenyl) phosphoniumchloride dicyclohexylmethyl(4-bromopheny1)(2-methylheptyl) phosphoniumchloride (Z-eth'ylhexyDpropyl(4-t-butylphenyl)heptylphosphonium bromidedihexylcyclopropylphenylphosphonium bromide allyl(cyclooct-2-enyl)(4-ethoxyphenyl) (4-methy1-3- penten-l-yDphosphonium bromidecycloheptyl(4-fluorophenyl)isoamylphosphonium chloride (Z-methylheptyl)cyclopropyl (4-nitrophenyl) cycloheptyl phosphonium chloridediisoamyl(3,4-diethylphenyl)phosphonium chloride(2,2,3,3-tetra'methylbutyl)isoamyl(4-phenoxyphenyl) cyclohexylphosphonium chloride (2-propylallyl) allyl (4-biphenyl) do decylphosphonium chlorideisoamyl(2,5-dimethylphenyl)pentyl(3,4,5-trimethylheptyl)phosphoniumchloride cyclopentylmethyl(2,4-dimethylphenyl) (Z-propylallyl)phosphonium chloride isoamyl p-propylphenyl) hexyl cyclooct-Z-enyl)phosphonium chloride cycl0heXylheXy1(2,6-dichlorophenyl)isoamylphosphonium chloridecyclohexyl(2,4-dichlorophenyl)isoamyl(iso-octenyl) phosphonium chloride3,4,5-trimethy1heptyl) Z-ethylhexyl) 3,4-dinitrophenyl)pentylphosphonium chloride tripentylphenylphosphonium chloridetrihexylphenylphosphonium chloride triheptylphenylphosphonium chloridetrioctylphenylphosphonium chloride triisoamylphenylphosphonium chloridetricyclopentylphenylphosphonium chloride tricyclohexylphenylphosphoniumchloride tricycloheptylphenylphosphonium chloridedipentylhexylphenylphosphonium chloride dipentylheptylphenylphosphoniumchloride dipentyloctylphenylphosphonium chloridedihexylpentylphenylphosphonium chloridetricyclohexylmethylphenylphosphonium chloridetri-(3,4,5-trimethylheptyl)phenylphosphonium chloridedihexyl(4-pentenyl)phenylphosphonium bromidetri-(2-propylallyl)phenylphosphonium chloridetri-(4-methyl-3-penten-1-yl)phenylphosphonium chloridetri-(Z-methylheptyl )phenylphosphonium chloridetri-(3-rnethylheptyl)phenylphosphonium chloridetri-(Z-ethylhcxyl)phenylphosphonium chloridetri-(2,2,3,3-tetramethylbutyl)phenylphosphonium.

chloride tri(cyclooct-2-enyl)phenylphosphonium chloride tri-(iso-octenyl) phenylphosphonium chloride EXAMPLE 16 Diheylp-trifluoromethylb enzyl phenylphosphonium chloride To 10.7 g. (0.04mole) of dihexylphenylphosphine suspended in 100 ml. of acetontrile isadded 9.7 g. (0.05 mole) of p-trifluoromethylbenzyl chloride in 75 ml.of acetonitrite. The reaction mixture is then heated at reflux for 24hours, cooled and evaporated to drynes in vacuo. The residue isdissolved in hexane:ether, treated with charcoal, filtered andconcentrated to dryness in vacuo to obtaindihexyl(p-trifluoromethylbenzyl)phenylphosphonium chloride Whenp-trifluoromethylbenzyl chloride in the above example is substituted bythe benzyl halides of Table I below, then the corresponding product isprepared.

Table I benzyl bromide benzyl chloride benzyl iodidep-trifluoromethoxybenzyl chloride p-trifluoroocetylbenzyl chlorideo-trifiuoromethylbenzyl chloride p-trifluoromethylsulfonylbenzylchloride o-chlorobenzyl chloride m-chlorobenzyl chloride p-chlorobenzylchloride 2,3-dichlorobenzyl chloride 2,4-dichlorobenzyl chloride2,5-dichlorobenzyl chloride 2,6-dichlorobenzyl chloride3,4dichlorobenzyl chloride 3,5-dichlorobenzyl chloride2,3,4-trichlorobnezyl chloride 2,3,5-trichlorobenzyl chloride2,3,6-trichlorobenzyl chloride 3,4,5-trichlorobenzyl chloridep-ditrifluoromethylsulfonyl-benzyl chloride p-bromobenzyl bromidem-nitrobenzyl chloride p-nitrobenzyl chloride p-cyanobenzyl chloride2,6-difiuorobenzyl chloride 2,4-dibromobenzyl bromide 2,4-difluorobenzylchloride 2-bromo-4-nitrobenzyl bromide 3,5-difiuorobenzyl chlorideo-fluorobenzyl chloride p-iluorobenzyl chloride2,6-dichloro-4-fluorobenzyl chloride Z-fluoro-4-trifiuoromethylbenzylchloride 4-fluoro-3-trifluoromethylbenzyl chloride u-methylbenzylchloride a-ethylbenzyl chloride a-methyl-p-chlorobenzyl chloridea-methyl-p-fiuorobenzyl chloride w-methyl-p-nitrobenzyl chlorideu-methyl-ZA-difluorObenzyl chloride u-methyl-p-trifluoromethylbenzylchloride d-methyl-p-bromobenzyl bromide EXAMPLE 17 When the procedure ofExample 16 is followed but ptrifluoromethylbenzyl chloride is replacedby the benzyl halides of Table 1, Example 16 and the tertiary phosphineis selected from Examples 2, 3, 4, 6, 10, 11, 12 and 13 24 then thecorresponding phosphonium salt is prepared. representative list of thephosphonium salts prepared 18 shown in Table 1, below.

Table I dipentylphenylbenzylphosphonium chloridedipentylphenylbenzylphosphonium bromide dipentylphenylbenzylphosphoniumiodide dihexylphenylbenzylphosphonium chloridediheptylphenylbenzylphosphonium chloride dinonylphenylbenzylphosphoniumchloride didecylphenylbenzylphosphoniurn chloridediundecylphenylbenzylphosphonium chloridedidodecylphenylbenzylphosphonium chloridediis0amylphenylbenzylphosphonium chloride di(2-methyl-1-butenyl)phenylbenzylphosphonium chloride dicyclooctylphenylbenzylphosphoniumchloride dicycloheptylphenylbenzylphosphonium chloridedicyclopentylphenylbenzylphosphonium chloridedicyclohexylphenylbenzylphosphonium chloridedicyclohexylmethylphenylbenzylphosphonium chloride di- (3,4,S-trimethylheptyl) phenylb enzylphosphonium chloridedi-(2-propylallyl)phenylbenzylphosphonium chloridedi-(4-methyl-3-penten-1yl)phenylbenzylphosphonium chloridedi-(Z-methylheptyl)phenylbenzylphosphonium chloridedi-(3-methylheptyl)phenylbenzylphosphonium chloride di- Z-ethylhexylphenylbenzylphosphonium chloride di- (2,2,3 ,3 -tetramethylb utylphenylbenzylpho sphonium chloridedi-(cyclooct-Z-enyl)phenylbenzylphosphonium chloride di- (iso-octenyl)phenylbenzylphosphonium chloride dioctyl(p-tolyl)benzylphosphoniumchloride dioctyl(p-bromophenyl) (p-bromobenzyl) phosphonium bromidedioctyl(p-chlorophenyl) (p-chlorobenzyl) phosphonium chloridedioctyl(p-nitrophenyl) (p-nitrobenzyl phosphonium chloridedioctyl(2,5-dimethylphenyl)benzylphosphonium chloridedioctyl(p-methoxyphenyl) (p-trifiuoromethylbenzyi) phosphonium chloridedioctyl(p-trifiuoromethylphenyl)benzylphosphonium chloridedioctyl(p-trifluoromethoxyphenyl)benzylphosphonium chloride dipentyl(p-chlorophenyl benzylphosphonium chloride dihexyl (pchlorophenyl)benzylphosphonium chloride diheptyl(p-chlorohenyl)benzylphosphoniumchloride diisoamyl(p-chlorophenyl) benzylphosphonium chloride di-(cyclohex-Z-enyl) (p-chlorophenyl) (p-chlorobenzyl) phosphonium chloridedicyclooctyl p-chlorophenyl) benzylphosphonium chloridedicycloheptyl(p-chlorophenyl)benzylphosphonium chloride dicyclohexyl(p-chlorophenyl) (2,4-difiuorobenzyl) phosphonium chloridedicyclohexylmethyl (p-chlorophenyl) (a-methylbenzyl) phosphoniumchloride diheptyl(p-tolyl)benzylphosphonium chloridedihepty1(p-nitrophenyl) benzylphosphonium chloride diisoamyl(p-methoxyphenyl) (p-methoxybenzyl) phosphonium chloridedicycloheptyl(p-trifluorornethylphenyl) (p-fluorobenzyl) phosphoniumchloride diisoamyl(p-methoxyphenyl)benzylphosphonium chlorided1decyl(p-biphenyl)benzylphosphonium chloride dipentyl (p-tolyl)benzylphosphonium chloride di-(cyclooct-2-enyl)(2,5-dimethylphenyl)benzylphosphonium chloride di-(cyclohex-Z-enyl)(p-tolyl)benzylphosphonium chloride dihexyl (p-bromophenyl)phosphoniumchloride dicyclohexyl(2-rnethyl-4-bromophenyl)benzylphosphonium chloridedi-(iso-octenyl) (p-tolyl)phosphonium chloridedicyclooctyl(p-nitrophenyl)benzylphosphonium chloridedidodecyl(p-phenoxyphenyl)benzylphosphonium chloride dicyclopenyl(p-trifluoromethoxyphenyl)phosphonium chloride diheptyl(p,p'-chlorobiphenyl)benzylphosphonium chloride di- Z-melhylheptyl)(p-rnethoxyphenyl) benzylphosphonium chloride dihexylphenylp-trifluoromethoxyb enzyl pho sphonium chloride dihexylphenylo-trifluoromethylb enzyl phosphonium chloridedihexylphenyl(o-chlorobenzyl)phosphonium chloridedihexylphenyl(m-chlorobenzyl)phosphonium chloridedihexylphenyl(p-chlorobenzyl)phosphonium chloride dihexylphenyl(2,3-dichlorobenzyl) phosphonium chloridedihexylhenyl(2,4-dichlorobenzyl)phosphonium chloride dihexylphenyl 2,5-dichlorobenzyl) phosphonium chloridedihexylphenyl(2,6-dichlorobenzyl)phosphoniurn chloride dihexylphenyl (3,4-dichlorobenzyl) phosphonium chloridedihexylphenyl(3,S-dichlorobenzyl)phosphonium chloride dihexylphenyl (2,3,4-trichlorobenzyl phosphonium chloride dihexylphenyl (2,3 S-trichlorobenzyl) pho sphonium chloride dihexylphenyl (2,3,6-trichlorobenzylphosphonium chloride dihexylphenyl 3,4,5 -trichlorobenzy1 phosphoniumchloride dihexylphenyl(p-ditri-fluorornethylsulfonylbenzyl) phosphoniumchloride dihexylphenyl(p-brornobenzyl)phosphonium bromidedihexylphenyl(rn-nitrobenzyl) phosphonium chloridedihexylphenyl(p-nitrobenzyl)phosphonium chloride dihexylphenyl(p-cyanobenzyl phosphonium chloride dihexylphenyl 2,'6-difluorobenzylphosphonium chloride dihexylphenyl(2,4-dibromobenzyl)phosphonium bromidedihexylphenyl(2,4-difluorobenzyl)phosphonium chloride dihexylphenyl2-bromo-4-nitrobenzyl) pho sphonium bromidedihexylphenyl(3,5-difluorobenzyl)phosphonium chloridedihexylpheriyl(o-fluorobenzyl) phosphonium chloridedihexylphenyl(pfluorobenzyl)phosphonium chloride dihexylphenyl(2,6-dichloro-4-fluorob enzyl) phosphonium chloridedihexylphenyl(2-fluoro-4-trifiuoromethylbenzyl) phosphonium chloridedhiexylphenyl(4-fluoro-3-trifluoromethylbenzyl) phosphonium chloridedihexylphenyl(a-rnethylbenzyl)phosphonium chloridedihexylphenyl(a-ethylbenzynphosphonium chloridedihexylphenyl(a-methyl-p-chlorobenzyl)phosphonium chloride dihexylphenyla-rnethyl-p-fluorobenzyl) phosphonium chloride dihexylphenyl(u-methyl-p-nitrobenzyl phosphonium chloride dihexylphenyl(a-methyl-2,4-difluorobenzyl) phosphonium chloridedihexylphenyl(a-rnethyl-p-trifluoromethylbenzyl) phosphonium chloridedihexylphenyl (a-methyl-p-brornobenzyl pho sphonium bromidediheXyl(2-chlorophenyl)benzylphosphonium chloridedihexyl(3-chlorophenyl)benzylphosphonium chloridedihexyl(4-chloropheny1)benzylphosphoniurn chloridedihexyl(2,3-dichlorophenyl)benzylphosphonium chloride dihexyl3,5-dichlorophenyl benzylphosphonium chloridedihexyl(3,4-dichlorophenyl)benzylphosphonium chloridedihexyl(4-ethoxyphenyl)benzylphosphonium chloridedihexyl(4-fiuorophenyl)benzylphosphonium chloridedihexyl(4-bromophenyl)benzylphosphonium chloridedihexyl(4-nitrophenyl)benzylphosphonium chloride dihexyl(4-phenoxyphenyl benzylphosphonium chloride dihexyl(4-trifluorornethylphenyl benzylpho sphonium chloridedihexyl(4-biphenyl)benzylphosphonium chloridedihexyl(4-phenoxyphenyl)benzylphosphonium chloridedihexyl(4-rnethylphenyl)benzylphosphoniurn chloridedihexyl(4-methoxypher1yl)benzylphosphonium chloridedihexyl(2,4-dichlorophenyl)benzylphosphonium chloridedihexyl(2,6-dichlorophenyl)benzylphosphonium chloridepentylhexylphenylbenzylphosphonium chloridedihexylphenylbenzylphosphonium chlorideheptylhexylphenylbenzylphosphoniurn chloridenonylhexylphenylbenzylphosphoniurn chloridedecylhexylphenylbenzylphosphonium chlorideundecylhexylphenylbenzylphosphoniu-rn chloridedodecylhexylphenylbenzylphosphonium chlorideisoamy1hexylphenylbenzylphosphonium chloride (Z-methyll-butenylhexylphenylb enzylphosphonium chloride(cyclohex-Z-enyl)hexylphenylbenzylphosphonium chloridecyclooctylhexylphenylbenzylphosphonium chloride pentyl 2-chlorophenyl)hexylbenzylphosphonium chloride pentyl(3-chlorophenyl)hexylbenzylphosphonium chloridepentyl(4-chlorophenyl)hexylbenzylphosphonium chloride pentyl 3 ,5-dichlorophenyl) hexylbenzylphosphonium chloride pentyl3,4-dichlorophenyl) hexylbenzylphosphonium chloridepentyl(4-t-butylphenyl)hexylbenzylphosphonium chloridepentyl(2,4-dimethylphenyl)hexylbenzylphosphonium chloridepentyl(4-ethoxyphenyl)hexylbenzylphosphonium chloridepentyl(4-fluorophenyl)hexylbenzylphosphonium chloridepentyl(2-brornophenyl)hexylbenzylphosphonium chloridepentyl(3-bromophenyl)hexylbenzylphosphonium chloridepentyl(4-bromophenyl)hexylbenzylphosphonium chloridepentyl(4-i-propylphenyl)hexylbenzylphosphonium chloridepentyl(2-methoxyphenyl)hexylbenzylphosphonium chloridepentyl(Z-nitrophenyl)hexylbenzylphosphonium chloridepentyl(4-nitrophenyl)hexylbenzylphosphonium chloridepentyl(4-phenoxyphenyl)hexylbenzylphosphonium chloride pentyl(4-trifluoromethylphenyl)hexylbenzylphosphonium chloridepentyl(4-biphenyl)hexylbenzylphosphonium chloride pentyl 4-phenoxyphenyl)hexylbenzylpho sphonium chloride pentyl (4-rnethylphenylhexylbenzylphosphonium chloridePentyl(2,4-diethylphenyl)hexylbenzylphosphonium chloridepentyl(3-rnethoxy)hexylbenzylphosphonium chloridepentyl(4-meihoxyphenyl)hexylbenzylphosphonium chloridepentyl(2,4-dichlorophenyl)hexylbenzylphosphonium chloridepentyl(2,6-dichlorophenyl)hexylbenzylphosphonium chloride heptyl(Z-nitrophenyl) isoamylb enzylphosphonium chloridecyclooctyl(2-bromophenyl)pentylbenzylphosphonium chloridecyclohexyl(2-chlorophenyl)undecylbenzylphosphonium chloride cyclohexyl(3,5-dichloropheny1)hexylbenzylphosphonium chloride cycloheptyl(Z-methoxyphenyl) (3-methylheptyl) benzylphosphonium chloridecyclohexyl(3-chlorophenyl) (cyclohex-2-enyl)benzy1- phosphonium chloride(cyclohex-Z-enyl) (4-methoxyphenyl)benzylphosphonium chloridecyclohexylmethyl(4-bromophenyl) (Z-methylheptyl) benzylphosphoniumchloride (Z-ethylhexyl) (4-t-butylphenyl)heptylbenzylphosphoniumchloride cycloheptyl(4-fiuorophenyl)isoamylbenzylphosphonium chloridenonyl(4-i-propylphenyl) octylbenzylphosphonium chloride (Z-methylheptyl)(4-nitrophenyl) cycloheptylbenzylphosphonium chloridedicyclopentyl(4-chlorophenyl)benzylphosphonium chloride isoamyl(2,3-dichlorophenyl) cyclohexylbenzylpho sphonium chlorideisoamyl(p-tolyl)benzylphosphonium chloride EXAMPLE 18-Dihexyloctylphenylphosphonium bromide 26 g.dihexyloctylphenylphosphonium chloride is added to 200 ml. of asaturated aqueous sodium bromide solution. The mixture is then heated to90, the solid is melted and the mixture is stirred for 5 min., cooled inan ice-bath and the water decanted. Another 200 ml. of saturated sodiumbromide solution is added and the procedure repeated. The ion exchangedphosphonium bromide is filtered, Washed with 1 liter of water followedby 2-200 ml. portions of hexane. The product is then heated twice with300 ml. of distilled water until a melt, cooled and the water decanted,triturated with hexane, and dried to obtaindihexyloctylphenylphosphonium bromide.

When the sodium bromide solution of the above example is replaced with asolution of an appropriate salt of Table I below, then the correspondingdesired phosphonium salt of Table II below is obtained.

Table 1' potassium oxalate potassium bromide sodium phosphate lithiumbromide sodium benzoate sodium methanesulfonate Table II sodium iodidesodium sulfate sodium nitrate sodium maleate sodium citrate sodiumacetate When the appropriate phosphonium salt is desired for any of thecompounds of this invention, then the above procedure may be used.

We claim:

1. A compound of the formula Where X and Y are hydrogen, halo,haloloweralkyl, nitro or haloloweralkoxy;

R, R and R" are a 5 to 12 carbon atom member which may be straightchained or branched and are alkyl or cycloalkyl;

R may also be cycloalkenyl, arloweralkyl or substituted benzyl of theformula where:

R, is hydrogen or loweralkyl;

R R R R and R are hydrogen, halo, haloloweralkyl,

nitro or haloloweralkoxy; and

A- is chloride, bromide, iodide, nitrate, phosphate or sulfate. 2. Acompound according to claim 1 where:

X and Y are hydrogen, fiuoro, chloro, bromo, trifluoromethyl, nitro ortrifluoromethoxy;

R, R and R" are amyl, hexyl, heptyl, octyl, cycloamyl,

cyclohexyl, cycloheptyl or cyclooctyl;

R may also be benzyl or substituted benzyl of the formula where:

R, is hydrogen or methyl;

R R R4,, R and R are hydrogen, fluoro, chloro, bromo,

trifluoromethyl, nitro or trifluoromethoxy; and

A- is chloride, bromide or iodide.

3. A compound according to claim 2.

where R, R and R" are octyl and A- is chloride thus formingtrioctylphenylphosphonium chloride. 4. A compound according to claim 2where X is p-fiuoro, R, R and R are octyl and A is chloride thus formingtrioctyl(p-tfluorophcnyDphosphonium chloride.

5. A compound according to claim 2 where X is p-trifluoromethyl, R, Rand R" are octyl and A- is chloride thus formingtrioctyl(p-trifluoromethyl) phosphonium chloride. 6. A compoundaccording to claim 2 where R and R" are octyl, R is benzyl and A- ischloride thus forming dioctylbenzylphenylphsphonium chloride. 7. Acompound according to claim 2 where R and R" are octyl, R is(p-fiuorobenzyl) and A- is chloride thus forming dioctyl(p-fluorobenzyl)phenylphosphonium chloride. 8. A compound according toclaim 2 where R and R are octyl, R is (p-trifluoromethylbenzyl) and A-is chloride thus formingdioctyl(p-trifluoromethylbenzyl)phenylphosphonium chloride. 9. Acompound according to claim 2 where R and R" are octyl, R is amyl and A-is chloride thus forming dioctylamylphenylphosphonium chloride. 10. Acompound according to claim 2 where R and R" are hexyl, R is amyl and Ais chloride thus forming dihexylamylphenylphosphonium chloride. 11. Acompound according to claim 2 where R' and R are octyl, R is(p-bromobenzyl) and X- is bromide thus forming dioctyl(p-bromobenzyl)phenylphosphonium bromide. 12. A compound according to claim 2 where Rand R" are octyl, R is (2,3,4,5,6-pentafiuorobenzyl) and X- is chloridethus forming dioctyl(2,3,4, 5,6-pentafluorobenzyl)phenylphosphoniumchloride. 13. A compound according to claim 2 where R, R and R" areheptyl and A- is chloride thus forming trlheptylphenylphosphoniumchloride.

14. A compound according to claim 2 where R, R and R are hexyl and A ischloride thus forming trihexylphenylphosphonium chloride. 15. A compoundaccording to claim 2 where R, R and R" are cyclohexyl and A- is chloridethus forming tricyclohexylphenylphosphonium chloride. 16. A compoundaccording to claim 2 where R, R and R are cycloheptyl and A- is chloridethus forming tricycloheptylphenylphosphonium chloride. 17. A compoundaccording to claim 2 where R and R" are heptyl, R is(2,6-dichlorobenzyl) and A is chloride thus formingdiheptyl(2,6-dichloro benzyl)phenylphosphonium chloride. 18. A compoundaccording to claim 2 where X is p-chloro, R and R are octyl, R is (2,6-dichlorobenzyl) and A" is chloride thus forming dioctyl(2,6dichlorobenzyl) (p chlorophenyl)phosphonium chloride. 19. A compoundaccording to claim 2 Where X is p-chloro, R and R are octyl, R is methyland A- is chloride thus forming dioctyl(a-methylbenzyl)(p-chlorophenyl)phosphonium chloride. 20. The compound of claim 1selected from the group consisting of dihexylpentylphenylphosphoniumchloride, dihexyloctylphenylphosphonium chloride,dihexylcyclopentylphenylphosphonium chloride, dihexyl Z-cyclopentenyl)phenylphosphonium chloride, dihexyl(2-cyclohexenyl)phenylphosphoniumchloride. 21. The compound of claim 1 selected from the group consistingof trioctyl(o-chlorophenyl)phosphonium chloride,triheXyl(m-chlorophenyl)phosphonium chloride,trihexyl(p-chlorophenyl)phosphonium chloride, trihexyl2,3-dichlorophenyl phosphonium chloride, trihexyl 2,4-dichlorophenyl)phosphonium chloride, trihexyl(2,5-dichlorophenyl)phosphonium chloride,trihexyl(2,6-dichlorophenyl)phosphonium chloride,trihexyl(2,4-dichlorophenyl)phosphonium chloride,trihexyl(3,5-dichlorophenyl)phosphonium chloride,trihexyl(2-bromophenyl)phosphonium chloride, trihexyl(3-bromophenyl)phosphonium chloride, trihexyl(4-bromophenyl)phosphonium chloride,trihexyl (4-trifluorome thylphenyl phosphonium chloride,

trihexyl(4-nitrophenyl)phosphonium chloride.

22. The compound of claim 1 selected from the group consisting ofdihexyl(o-chlorobenzyl)phenyl phosphonium chloride,

dihexyl(m-chlorobenzyl)phenyl phosphonium chloride,

dihexyl(p-chlorobenzyl)phenyl phosphonium chloride,

dihexyl(2,3-dichlorobenzyl)phenyl phosphonium chloride,

dihexyl(2,4-dichlorobenzyl) phenyl phosphonium chloride,

dihexyl(2,5-dichlorobenzyl) phenyl phosphonium chloride,

dihexyl (2,6-dichlorobenzyl) phenyl phosphonium chloride,

dihexyl(3,4-dichlorobenzyl)phenyl phosphonium chloride,

dihexyl 3 ,5 -dichlorobenzyl phenyl phosphonium chloride,

dihexyl(2,3,4-trichlorobenzyl) phenyl phosphonium chloride,

dihexyl(2,3,5-trichloroberizyl) phenyl phosphonium chloride,

dihexyl(2,3,6-trichlorobenzyl)phenyl phosphonium chloride,

dihexy1( 2,4,5-trichlorobenzyl)phenyl phosphonium chloride,dihexyl(2,4,6-trichlorobenzyl)phenyl phosphonium chloride,dihexyl(3,4,5-trichlorobenzyl)phenyl phosphonium chloride.

References Cited UNITED STATES PATENTS 3,230,069 1/1966 Preston 260606.5F 1,921,364 8/1933 Lommet et a1. 260606.5 F 2,102,103 12/1937 Urbain etal. 260-606.5 F 2,914,522 11/1959 Ramirez 260-6065 F 3,235,592 2/1966Wilson et al. 260-606.5 F 3,243,450 3/1966 Grayson 260606.5 F 3,268,3238/1966 Goyette 260606.5 F

OTHER REFERENCES Kosolapofi, Organophosphorus Compounds (1950), NewYork, John Wiley & Sons, Inc., pp. 86-93 and 330-1.

WERTE-N F. W. BELLAMY, Primary Examiner US. Cl. X.R. 424-210, 198

